WO2002072694A1 - Composition de precurseur de resine fluoree echangeuse d'ions - Google Patents

Composition de precurseur de resine fluoree echangeuse d'ions Download PDF

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Publication number
WO2002072694A1
WO2002072694A1 PCT/JP2002/001197 JP0201197W WO02072694A1 WO 2002072694 A1 WO2002072694 A1 WO 2002072694A1 JP 0201197 W JP0201197 W JP 0201197W WO 02072694 A1 WO02072694 A1 WO 02072694A1
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Prior art keywords
dispersion
polymerization
fluorine
exchange resin
ptfe
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PCT/JP2002/001197
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English (en)
Japanese (ja)
Inventor
Takuya Hasegawa
Yoshimichi Nakayama
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Priority to US10/467,281 priority Critical patent/US6911482B2/en
Priority to JP2002571593A priority patent/JP3920779B2/ja
Publication of WO2002072694A1 publication Critical patent/WO2002072694A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1083—Starting from polymer melts other than monomer melts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1088—Chemical modification, e.g. sulfonation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/109—After-treatment of the membrane other than by polymerisation thermal other than drying, e.g. sintering
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for producing a fluorine-based ion exchange membrane used as an electrolyte and a diaphragm of a solid polymer electrolyte fuel cell, and in particular, an intermediate raw material of a fluorine-based ion exchange membrane having excellent performance as an electrolyte and a diaphragm,
  • the present invention relates to a method for producing a precursor composition.
  • a fuel cell is a kind of power generator that extracts electric energy by electrochemically oxidizing a fuel such as hydrogen / methanol, and has recently attracted attention as a clean energy supply source.
  • Fuel cells are classified into phosphoric acid type, molten carbonate type, solid oxide type, solid polymer electrolyte type, etc., depending on the type of electrolyte used. Among them, solid polymer electrolyte type fuel cells have standard operating temperatures. However, since its energy density is as low as 1 oo ° C or less and its energy density is high, it is expected to be widely used as a power source for electric vehicles.
  • the basic structure of a solid polymer electrolyte fuel cell consists of an ion exchange membrane and a pair of gas diffusion electrodes joined to both sides of the membrane, supplying hydrogen to one electrode and oxygen to the other, and applying an external load between the two electrodes.
  • the power is generated by connecting to a circuit. More specifically, protons and electrons are generated at the hydrogen-side electrode, and the protons move inside the ion-exchange membrane to reach the oxygen-side electrode, and then react with oxygen to generate water.
  • the electrons flowing out of the hydrogen-side electrode through the lead wire, after the electric energy is extracted in the external load circuit further reach the oxygen-side electrode through the lead wire and contribute to the progress of the water generation reaction. Will do.
  • the first characteristic required for the ion exchange membrane is high ion conductivity, but it is thought that when protons move inside the ion exchange membrane, water molecules are hydrated and thus become stable. Therefore, high ion conductivity and high water content and water dispersibility are important required characteristics.
  • the ion exchange membrane functions as a barrier for preventing a direct reaction between hydrogen and oxygen, low permeability to gas is required.
  • Other required characteristics include strong oxidizing atmosphere during fuel cell operation. Chemical stability to withstand the heat, mechanical strength to withstand further thinning, and the like.
  • fluorine ion exchange resins are widely used because of their high chemical stability.
  • “Naphion (registered trademark)” manufactured by Dubon having a sulfonic acid group at a chain end is widely used.
  • Such a fluorine ion exchange resin has generally well-balanced properties as a solid polymer electrolyte material. As the battery has been put into practical use, further improvements in physical properties have been required.
  • Japanese Patent Application Laid-Open No. Sho 53-14981 discloses a method for forming a fibrinolized four-foil.
  • a reinforced cation exchange resin characterized in that a chemically modified ethylene polymer is mixed into a cation exchange resin body forming a cation exchange resin membrane.
  • the production method disclosed in the publication includes: a) an ion-exchange resin precursor or a product obtained by swelling the precursor with trichloromouth trifluoroethane; b) a polytetrafluoroethylene polymer obtained by emulsion polymerization or suspension polymerization (hereinafter, referred to as “polymerization”). (Hereinafter, referred to as PTFE)) and a fine powder or an aqueous emulsified dispersion, and then melt-kneaded to obtain a composition.
  • PTFE polytetrafluoroethylene polymer obtained by emulsion polymerization or suspension polymerization
  • Japanese Patent Publication No. 63-613337 discloses a method of drawing a film made of a fluorinated ion-exchange resin containing a fluororesin fibrillated fiber uniformly dispersed therein at a specific temperature to form a thin film.
  • PTFE aggregates are generated inside the membrane, and irregularities are likely to be generated on the sheet surface. like this It is particularly difficult to produce a thin film when such irregularities occur.
  • the publication describes that a smoothing treatment by a roll press or the like is performed before the thin film is drawn by stretching.
  • Japanese Patent Publication No. S61-168288 discloses such a roll pressing method.
  • Sho 533-149881, Japanese Patent Publication No. Sho 63-63133 and Japanese Patent Publication No. Sho 61-168288 disclose such methods.
  • Conventional technologies are limited to simple addition of PTFE, and are particularly useful in industrial applications as ion exchange membranes for fuel cells due to the difficulty of uniform dispersion of PTFE, good melt molding, and effective use of PTFE. Technology could not be.
  • JP-A-2001-2980000 was prepared by using an aqueous dispersion containing at least three essential components of a fluororesin fine particle, an ion-exchange polymer, and a fluorinated surfactant.
  • An ion exchange membrane is disclosed.
  • three essential components are mixed: an aqueous suspension of fluororesin fine particles, a solution of an ion-exchangeable polymer, and a solution of a fluorinated surfactant.
  • This publication describes the use of an ion-exchangeable polymer solution as a feature of the present invention, and therefore does not make any description concerning cleaning which is indispensable when using a fluorine-based ion-exchange resin precursor dispersion. . Furthermore, there is no description that these aqueous suspensions and solutions were directly obtained from each polymerization solution in the polymerization step without isolating or aggregating resin solids.
  • the publication describes that the solution is prepared by using an ion-exchange polymer solution as a solvent and using water, an organic solvent, or the like. It can be considered to have been prepared using isolated or aggregated ion exchangeable polymers.
  • An object of the present invention is to provide a method for producing a fluorine-based ion exchange resin precursor composition having excellent mechanical strength and melt moldability.
  • the problem with the PTFE dispersion in the prior art is considered to be one of the reasons that the mutual contact between the ion-exchange tree precursor shown in the above a) and the PTFE shown in b) was not sufficient.
  • the present inventors have found that a highly uniform dispersion can be achieved by mixing a specific fluorinated ion-exchange resin precursor dispersion and a PTFE dispersion.
  • the present inventors have found that the fluorinated ion-exchange resin precursor composition thus produced is excellent in melt moldability, and that a high-quality sheet can be produced particularly in extrusion sheet molding, and the present invention has been accomplished.
  • the present invention comprises a step of mixing a fluorinated ion exchange resin precursor dispersion and a PTFE dispersion, and a step of removing a liquid component from the mixture.
  • the present invention relates to a method for producing the composition.
  • FIG. 1 shows the results of the fuel cell characteristic test of Example 6.
  • FIG. 2 shows the results of the fuel cell characteristic test of Example 9.
  • the ion-exchange membrane can be formed by forming an ion-exchange resin precursor having melt moldability (thermoplasticity) into a membrane, and then generating an ion-exchange group by a hydrolysis treatment.
  • CF 2 CF— O (OCF 2 CFLO) n — (CF 2 ) m -W
  • a fluorinated fluorinated compound represented by the general formula CF 2 CFZ.
  • L is an F atom or a perfluoroalkyl group having 1 to 3 carbon atoms
  • n is an integer of 0 to 3
  • m is an integer of 1 to 3
  • Z is H, C1, F or 1 to 3 carbon atoms.
  • Perfluoroalkyl group, W is hydrolyzed
  • C0 2 H or S0 3 functional groups can be converted to H, S_ ⁇ 2 F, S0 2 C 1 as such functional groups, S_ ⁇ 2 B r, COF, COC l , COB r, C0 2 CH 3 , CO 2 C 2 H 5 is usually preferably used.
  • S_ ⁇ 2 F, S0 2 C 1 as such functional groups
  • S_ ⁇ 2 B r, COF, COC l , COB r, C0 2 CH 3 , CO 2 C 2 H 5 is usually preferably used.
  • Such a fluorine ion exchange resin precursor can be synthesized by a conventionally known means. For example, a method of using a polymerization solvent such as a fluorine-containing hydrocarbon, filling and dissolving the above-mentioned vinyl fluoride compound and olefin fluoride gas to cause a reaction (solution polymerization), and using a solvent such as a foam.
  • a polymerization solvent such as a fluorine-containing hydrocarbon
  • PTFE can also be synthesized by conventionally known means. That is, suspension polymerization, emulsion polymerization, miniemulsion polymerization, microemulsion, and the like performed in an aqueous medium. Polymerization, and solution polymerization using a polymerization solvent such as a fluorinated hydrocarbon. In the present invention, among these, those prepared by the polymerization method of misalignment can be used. Examples of the fluorinated hydrocarbon used as the polymerization solvent for solution polymerization include, for example, trichloro mouth trifluorofluoroethane and 1,1,1,2,3,4,4,5,5,5-decafluoropentane. A group of compounds generically referred to as "fluorocarbons" can be suitably used. As described later, in the present invention, a dispersion obtained after the above polymerization reaction can be used as it is as a PTFE dispersion.
  • Both the fluorinated ion-exchange resin precursor and PTFE obtained by the polymerization method are present in a state of being dispersed in liquid components such as fluorinated hydrocarbons, residual monomers, and water at the end of the polymerization. .
  • these dispersions can be used as they are without substantially isolating the polymer component from these dispersions.
  • the dispersion referred to in the present invention usually refers to the dispersion itself after the polymerization reaction in many cases. However, other dispersion media may be added as needed, and such dispersion media may be added as necessary. The addition may be further advanced, and the initial dispersion medium may be replaced with another dispersion medium.
  • the polymerization method includes polymerization using a non-aqueous medium (hereinafter, referred to as non-aqueous polymerization: solution polymerization, bulk polymerization, etc.) and polymerization using an aqueous medium (hereinafter, referred to as water-based polymerization: emulsion polymerization, mini polymerization). Emulsion polymerization, microemulsion polymerization, suspension polymerization, etc.).
  • non-aqueous polymerization solution polymerization, bulk polymerization, etc.
  • water-based polymerization emulsion polymerization, mini polymerization
  • Emulsion polymerization, microemulsion polymerization, suspension polymerization, etc. when the polymerization method of the precursor dispersion of the fluorinated ion exchange resin and the polymerization method of the p TFE dispersion belong to the same mode, the dispersion media have good compatibility, and when both are mixed, the dispersion is highly uniform.
  • the mode of the polymerization method belongs to the non-aqueous polymerization
  • the expansion of the polymer molecular chain in the dispersion is generally larger than that of the aqueous polymerization. More preferred.
  • a polymerization solvent suitable for such non-aqueous polymerization a fluorinated hydrocarbon can be exemplified.
  • the polymerization method of the fluorinated ion exchange resin precursor dispersion and the PTFE dispersion belong to different modes, the affinity between the dispersion media is poor, so that the dispersion is generally uniform. It is expected that mixing is difficult.
  • the present inventors have found that, even in a case where the mode of the polymerization method is a mixture of dispersions different from each other, in many cases, an emulsion dispersion is formed, and good mixing can be achieved.
  • a dispersion prepared by aqueous polymerization usually contains an emulsifier, an auxiliary emulsifier, a suspension stabilizer, etc., unlike a single dispersion medium containing no such, a good dispersion is obtained. It can be inferred that mixing stability could be shown. In the present invention, mixing stability can be improved by further adding an emulsifier, an auxiliary emulsifier, a suspension stabilizer, a water-soluble polymer, or the like, if necessary.
  • the present invention is characterized by the use of a dispersion of a fluorinated ion-exchange resin precursor, which does not exhibit strong acidity, so that even when mixed with a PTFE dispersion, it can be mixed well without causing aggregation of PTFE. It can be carried out. That is, the amount of the surfactant in the present invention is the amount of the emulsifier previously mixed in the PTFE dispersion in order to emulsify the PTFE fine particles, and in many cases, it is sufficient and the surfactant added as necessary It should be considered that the agent is added not for stabilizing the PTFE fine particles but for promoting the emulsification of the solvents.
  • the solid content ratio in the fluorinated ion-exchange resin precursor dispersion is 1 to 99%, preferably 2 to 50%. If the solid content ratio is less than 1%, it is not preferable because it takes time to remove liquid components after mixing. If the solid content ratio is more than 99%, the viscosity becomes too high and mixing becomes difficult, which is not preferable.
  • the dispersion liquid of the fluorine-based ion-exchange resin precursor may be used by adding another dispersion medium stabilizer and the like, if necessary.
  • the average diameter of the polymer in the fluorine-based ion exchange resin precursor dispersion is preferably 50 ⁇ or less, more preferably 10 ⁇ or less.
  • the solid content ratio in the PTFE dispersion is 1 to 99%, preferably 2 to 50%. If the solid content ratio is less than 1%, it is not preferable because it takes time to remove the liquid component after mixing. If the solid content ratio is more than 99%, the viscosity becomes too high and mixing becomes difficult.
  • the PTFE dispersion can be used as it is when the mixing stability with the fluorinated ion exchange resin precursor dispersion is good. If the mixing stability is not sufficient, for example, a stabilizer such as a surfactant is added, and a dispersion medium compatible with the dispersion medium of the fluorine-based ion-exchange resin precursor dispersion is added to the emulsion to form an emulsion.
  • the dispersion stability 14 is not impaired during the operation.
  • the average diameter of the polymer in the PTFE dispersion is preferably 50 Xm or less, more preferably 10 ⁇ m or less.
  • the surface of the PTFE particles present in the dispersion is coated in advance with a fluorinated ion exchange resin precursor, etc. It is preferable because good dispersibility of PTFE in the precursor composition can be obtained. Examples of such embodiments include a method of adding the fluorinated compound of the present invention to the late stage of the polymerization of PTFE, and a method of adding fluorinated ion exchange resin precursor in advance and polymerizing PTFE.
  • any conventionally known method can be used.
  • a fluorinated ion-exchange resin precursor dispersion and a PTFE dispersion are introduced into a closed vessel having a stirring blade, and this is often used. It can be mixed by stirring.
  • the stirring is usually performed at a temperature equal to or lower than the boiling point of the dispersion medium, and is preferably performed at a temperature of o ° C to room temperature. It is necessary to adjust the stirring time and stirring speed depending on the viscosity of the mixed liquid, etc., but by adjusting the solid content ratio of both dispersion liquids, it is possible to perform uniform mixing within a few minutes or less. You.
  • the mixing ratio of the two dispersions can be adjusted according to the purpose, but the weight of PTFE is preferably 0.1% to 50% with respect to the weight of the fluorine-based ion exchange resin precursor, 2% to 25% is more preferred, and 0.3% to 10% is even more preferred.
  • any conventionally known method can be used. For example, a method of adding a substance having a dispersion rupture effect to a mixed dispersion to precipitate a solid content, a method of distilling a liquid component by stirring the mixed dispersion under heating, and the like. It can be suitably used.
  • the substance having a dispersion breaking action any substance that reduces the affinity of the solid with the dispersion medium can be used.
  • general substances such as alkanol, alkane, ketone, ether, and methylene chloride can be used. Any organic solvent can be used.
  • the liquid component can be satisfactorily distilled by using a paddle dryer under heating.
  • fluorine-containing hydrocarbons having a low boiling point can be distilled off under normal pressure, but residual monomers having a high boiling point and the like are preferably distilled off under reduced pressure.
  • the solid content is sufficiently washed by further adding a fluorine-containing hydrocarbon and repeating the above operation several times. Is preferred.
  • melt-kneading the composition a method generally known as a melt-kneading method such as kneading between two rolls, kneading with a Banbury mixer, kneading with an extruder, or the like can be used. Any of them can be suitably used.
  • a high PTFE content composition with a PTFE content of more than 25% the final PTFE content can be reduced by melt-kneading it with a fluorinated ion exchange resin precursor. It is.
  • a method it is possible to prepare a high PTFE content composition in advance and use it as a masterbatch while diluting it with a fluorinated ion exchange resin precursor. It is particularly suitable.
  • the composition of the present invention has a significantly better uniform dispersibility than conventional compositions without melt-kneading, it is not essential to melt-knead before melt-molding. That is, by using an appropriate equipment such as a ram extruder, it is possible to perform melt molding without substantially kneading the composition.
  • a yarn and composition which is melt-formed without substantial kneading since the formation of fibrils in PTFE is suppressed, it is necessary to further suppress abnormal viscosity (sharkskin, melt fracture, etc.) during melt-forming. It is particularly useful for such purposes.
  • PTFE uniformly dispersed by various post-processing (stretching, rolling, etc.) after film formation can be sufficiently subjected to fibrillation.
  • the molecular weight of the PTFE according to the present invention is not particularly limited, but is suitably from 100,000 to 20,000,000, more preferably from 200,000 to 100,000,000, more preferably from 300,000 to 600,000. It is generally known that PTFE having a molecular weight of 1,000,000 or more easily changes into fibrils due to shear stress. It is known that such fibrillation becomes remarkable at a temperature higher than the crystal transition temperature (20 ° C). For example, if it is desired to reduce the fibrillation during mixing of the dispersion, room temperature The dispersion can be mixed at a low temperature below, preferably below the crystal transition temperature.
  • Molding methods such as melt molding (T-die method, inflation method, calendar method, etc.) and casting method are used to mold the fluorinated ion exchange resin precursor composition into a film. Any of the methods generally known as can be suitably used.
  • a casting method a dispersion of the composition is formed into a sheet and then the dispersion medium is removed, or a fluorine-based ion-exchange resin is hydrolyzed to form a fluorine-based ion-exchange resin precursor composition. After forming a resin composition and dissolving or dispersing it in water or a water-Z alcohol mixture, the solution may be formed into a sheet and the solvent may be removed.
  • the resin temperature at the time of performing the melt molding by the T-die method is preferably from 100 to 300 ° C, more preferably from 200 to 280 ° C. C.
  • the resin temperature at the time of melt molding by the inflation method is 100 to 300. C is preferred, and more preferably 160 to 240 ° C.
  • the sheet melt-formed by these methods is cooled to a temperature below the melting temperature by using a cooling port or the like.
  • the film formed by the combination of the ram extrusion and the slit die is subjected to various post-processing (stretching, rolling, and the like) after the film formation so that the PTFE is sufficiently fibrillated.
  • the sheet is hydrolyzed to obtain a fluorine-based ion exchange membrane.
  • a method of hydrolysis for example, as described in Japanese Patent No. 2753371, the ion exchange group precursor of the sheet is converted into a metal salt type ion exchange group using an alkali hydroxide solution. , can then be used a conventionally known method of converting the ion exchange groups of the acid type (S 0 3 H or C 0 2 H) with an acid such as sulfonic acid or hydrochloric acid. Such transformations are well known to those skilled in the art and are described in embodiments of the present invention.
  • a hydrothermal treatment can be performed after the hydrolysis step, if necessary.
  • the ion-exchange membrane is subjected to swelling treatment by heating in water or an organic solvent soluble in water, and then returned to the acid form. It is possible to use an ion exchange membrane with a high water content.
  • the equivalent weight (EW) of the fluorine-based ion exchange membrane of the present invention is not particularly limited, but is preferably 400 to 140, more preferably 600 to 1200.
  • the thickness of the fluorine-based ion exchange membrane of the present invention is 1 to 500 m, preferably 5 to 100 ⁇ , more preferably 10 to 50 / m. If the film thickness is smaller than 1 ⁇ , the above-mentioned inconveniences are likely to occur due to diffusion of hydrogen and oxygen, and the film may be damaged due to differential pressure, strain, etc. during handling during fuel cell operation or fuel cell operation. Inconvenience is likely to occur. Further, a membrane having a thickness greater than 500 / zm generally has low ion permeability, and thus does not have sufficient performance as an ion exchange membrane.
  • the PTFE dispersity of the fluorine-based ion exchange membrane of the present invention is preferably 0.8 or more, more preferably 0.9 or more, further preferably 0.95 or more, and still more preferably 0.98 or more.
  • the amount of PTFE that actually contributes to mechanical strength in the matrix decreases, so that even if the same weight of PTFE is added, only a low degree of dispersion can be obtained. Absent.
  • MEA membrane electrode assembly
  • the electrode is composed of fine particles of a catalytic metal and a conductive agent supporting the catalytic metal, and contains a water repellent as required.
  • the catalyst used for the electrode is not particularly limited as long as it is a metal that promotes the oxidation reaction of hydrogen and the reduction reaction by oxygen. Platinum, gold, silver, palladium, iridium, rhodium, ruthenium, iron, covanolate, nickele , Chromium, tungsten, manganese, vanadium or alloys thereof. Among them, platinum is mainly used.
  • the conductive agent may be any conductive material, for example, various metals and carbon materials.
  • the carbon material include carbon black such as furnace black, channel black, and acetylene black, activated carbon, and graphite. These may be used alone or in combination.
  • As the water repellent a fluorine-containing resin having water repellency is preferable, and one having excellent heat resistance and oxidation resistance is more preferable. Les ,. Examples thereof include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer.
  • an electrode manufactured by E-TEK is widely used.
  • E-TEK an electrode manufactured by E-TEK
  • the following method is performed. Platinum-supporting carbon as an electrode substance is dispersed in a solution of a fluorinated ion exchange resin in a mixed solution of alcohol and water to form a paste. A certain amount of this is applied to a PTFE sheet and dried. Next, the application surfaces of the PTFE sheet are faced to each other, an ion exchange membrane is interposed therebetween, and the sheets are joined by a hot press.
  • the hot pressing temperature depends on the type of ion exchange membrane, but is usually 100. C or higher, preferably 130 ° C or higher, more preferably 150 ° C or higher.
  • ME A Other manufacturing methods for ME A include ⁇ J. Elec t r o c em.
  • a solid polymer electrolyte fuel cell is composed of a MEA, a current collector, a fuel cell frame, a gas supply device, and the like.
  • the collector (bipolar plate) is a graphite or metal flange that has a gas flow path on the surface, etc. In addition to transmitting electrons to an external load circuit, it also transfers hydrogen and oxygen to the MEA surface. It has a function as a supply channel. Fuel cells can be created by inserting multiple MEAs between these current collectors and stacking them.
  • the operation of a fuel cell is performed by supplying hydrogen to one electrode and oxygen or air to the other electrode.
  • the reinforced ion exchange membrane as in the present invention may be able to operate at 100 ° C. to 150 ° C. by improving the high temperature and humidity strength.
  • the melt index of the fluorinated ion-exchange resin precursor measured at a temperature of 270 ° C. and a load of 2.16 kg was defined as MI (g / 10 min) based on JISK-7210.
  • the diameter of the strand extruded from the orifice was measured with a vernier caliper, and the increment with respect to the diameter of the orifice was defined as a percentage (%).
  • the remaining dispersion after fractionation is 16.00 kg, and the solid content ratio is HCFC-141 as a dispersion medium.
  • 4.6 wt% PTFE dispersion (Daikin Lubn (registered trademark) LD-1E : Solution polymerization) 1. 58 kg was stirred and mixed at room temperature. These dispersions were well mixed to form a mixed dispersion.
  • CFC-113 and HCFC-141b were distilled off from the mixed dispersion under normal pressure while heating at 90 ° C using a rotary paddle-type horizontal paddle dryer.
  • the remaining monomer was distilled off under reduced pressure while heating at 90 ° C. 1.41 kg of a fluorine-based ion-exchange resin precursor composition was obtained.
  • the resulting composition was washed with 3 liters of CFC-113. This was repeated three times. It was further dried at a reduced pressure of 110 ° C for 16 hours. Finally, 1.34 kg of solids were obtained. This solid content The equivalent weight was 998, the melt index was 15.1, the spall was 16%, and the critical cutting speed was 200 / sec. The solid content was further reduced to 285 using a batch-type melt kneader (Plastmill, manufactured by Toyo Seiki). The mixture was kneaded at 100 rpm for 30 minutes. The melt kneaded product had a melt index of 15.8, a spall of 12%, and a critical shear rate of 200 nosec.
  • the melt-kneaded product had a melt index of 13.7, a swell of 16%, and a critical shear rate of 175 / sec.
  • the solid matter before and after the melt kneading was press-formed at 270 ° C and 2 OMPa to obtain a film having a thickness of about 200 ⁇ m. All the films were homogeneous, and the presence of PTFE aggregates and the like was not observed under a 200-fold optical microscope.
  • Example 3 (high molecular weight PTFE: solvent precipitated methanol)
  • Fluorinated ion-exchange resin precursor dispersion of Example 1 was dispersed in 15.00 kg of PTFE dispersion having a solid content ratio of about 60 wt% using water as a dispersion medium (Daikin polyflon (registered trademark) (Trademark) D-2 C: Emulsion polymerization) 110 g was calorie-mixed and agitated and mixed to obtain 15.1 kg of a homogeneous mixed dispersion. Next, the same volume of methanol was added to the mixed dispersion, followed by stirring and mixing. By mixing, the mixed dispersion became a white swollen slurry. After leaving the swollen slurry to settle, the supernatant was removed.
  • a dispersion medium Daikin polyflon (registered trademark) (Trademark) D-2 C: Emulsion polymerization
  • This solid was press-molded at 270 ° C. and 2 OMPa to obtain a film having a thickness of about 200.
  • the film was homogeneously dispersed in PTFE and became cloudy. The presence of aggregates of PTFE and the like was not observed by optical microscope observation at 200 times.
  • the CFC-11 and the remaining monomer were distilled off from the mixed dispersion under reduced pressure while heating at 90 ° C. using a horizontal paddle drier of a rotary blade stirring type to obtain a powder.
  • This powder was washed with 5 liters of CFC-113, and dried under reduced pressure at 110 ° C. for 16 hours to obtain 1.1 kg of a solid content of a fluorinated ion exchange resin precursor composition.
  • the equivalent weight of this solid was 995, the melt index was 16.0, and the concentration of PTFE contained was 4.5 wt%.
  • This solid was press-molded at 270 ° C. and 2 OMPa to obtain a film having a thickness of about 200 ⁇ .
  • Example 5 High molecular weight PTFE: melt kneading 10 minutes
  • Example 4 100 g of the solid content obtained in Example 4 was kneaded at 270 ° C. and 50 rpm for 10 minutes using a batch-type melt kneader (Blast Minore manufactured by Toyo Seiki). The equivalent weight of the melt-kneaded product was 1002, the melt index was 0.55, and the spel was 135%.
  • This solid was press-molded at 270 ° C. and 2 OMPa to obtain a film having a thickness of about 200 im. The film was homogeneous, and the presence of PTFE aggregates and the like was not observed under light microscope observation at a magnification of 200 times.
  • the solvent was volatilized with dry nitrogen while stirring 1707 g of the same PTFE dispersion used in Example 1. In this process, the solid content became a powder through a paste. Next, this powder was dried at 110 ° C. under reduced pressure for 16 hours. Finally, 79 g of solids were obtained. Then, 5 g of the above-mentioned PTFE powder was added to 95 g of a pellet of a fluorine-based ion exchange resin precursor having an equivalent weight of 950 and a melt index of 20, and mixed well. Next, the mixture was kneaded at 270 ° C. and 50 rpm for 30 minutes using a batch-type melt kneader (Plastmill manufactured by Toyo Seiki). The equivalent weight of the melt-kneaded product was 998, the melt index was 12.3, the spel was 9%, and the critical shear rate was 75 / sec.
  • a batch-type melt kneader Plastmill manufactured by Toyo Seiki
  • melt-kneader Pullastmill manufactured by Toyo Seiki
  • the equivalent weight of the melt-kneaded product was 100, the melt index was 0.32, and the spel was 13.6%.
  • the solid was press-molded at 270 ° C. and 2 OMPa to obtain a finolem having a thickness of about 200 / m.
  • the film was heterogeneous, and the presence of PTFE aggregates and the like was observed at a magnification of 200 times with an optical microscope.
  • a melt-kneaded product was prepared in the same manner as in Comparative Example 3, except that the kneading time was changed to 10 minutes.
  • the equivalent weight of the melt-kneaded product was 1 000, the melt index was 0.33, and the swelling was 122%.
  • the solid was press-molded at 270 ° C. and 2 OMPa to obtain a film having a thickness of about 200 / m.
  • the film was heterogeneous, and the presence of PTFE aggregates and the like was observed at a magnification of 200 times with an optical microscope.
  • Comparative Example 5 (mixing with a completely solid fluorinated ion-exchange resin precursor)
  • the same fluorine-based ion-exchange resin precursor powder as in Comparative Example 1 was added to 20 g of 200 ml of CFC—113.
  • the mixture was refluxed for 8 hours, and then cooled to obtain about 40 g of a powder swollen with CFC-11.
  • the mixed dispersion was dried at 90 ° C.
  • DMSO: KOH: water 5: 30: 65
  • MEA was prepared by pressing at 50 ° C. and a pressure of 50 kgZcm 2 for 90 seconds.
  • the MEA was incorporated into a fuel cell single cell evaluation apparatus, and a fuel cell characteristic test was performed at 70 ° C. under normal pressure using hydrogen gas and oxygen gas. Hydrogen was supplied at 85 ° C and oxygen was supplied at 70 ° C.
  • Figure 1 shows the results of the characteristic test.
  • FIG. 1 also shows a characteristic test result when an ion exchange membrane was similarly prepared using the fluorine-based ion exchange resin precursor of Comparative Example 1, a fuel cell was assembled, and a characteristic test was performed. ing.
  • DMSO: KOH: water 5:30:65
  • the film of Example 4 the film of Example 5, the film obtained by the same method as in Example 4 from the pellet of Comparative Example 1, and the film of Comparative Example 4, the film thickness and the haze before and after hydrolysis were measured, respectively. did.
  • the haze was measured based on JIS K7105 using a reflectance transmittance meter HR-100 type (manufactured by Nagami Color Research Laboratory). Table 1 shows the measurement results. Since the fluorinated ion exchange resin precursor composition according to the present invention has a high dispersibility of PTFE, when it is made to have a thickness of about 200 m, it becomes milky white as a whole.
  • the fluorine-based ion-exchange resin precursor composition according to the prior art has a high transparency even at a thickness of about 200 ⁇ due to low dispersibility of PTFE. Furthermore, when the composition according to the present invention and the composition according to the prior art were compared for a film obtained from a melt-kneaded mixture for the same time (here, 10 minutes), a large number of PTF / aggregates were visually confirmed in the composition according to the prior art. On the other hand, such ⁇ TF ⁇ aggregates are not observed in the composition of the present invention.
  • One of the characteristics of the composition of the present invention is that the composition of the present invention shows a higher haze than the composition of the prior art, reflecting the above-mentioned high PTF dispersibility and high utilization efficiency.
  • Example 4 (Invention: not kneaded) 1 97 92. 9 29.2
  • Example 5 (Invention: kneading for 10 minutes) 200 92. 1 30.8 Comparative Example 1 (without PTFE) 1 78 97.1 1. 7 Comparative Example 4 (Conventional technology: kneading for 10 minutes) 258 92.2 13.7
  • Example 4 (Invention: not kneaded) 201 89. 9 45.0
  • Example 5 (Invention: 10-minute kneading) 249 83. 46.5.2 Comparative Example 1 (without PTFE) 275 95.9.2.9 Comparative Example 4 (Prior art: kneading for 10 minutes) 302 91.2 11.7, Tt: total light transmittance, H: haze
  • Example 9
  • Example 7 Contain 3 wt% of PTFE of Example 1 and 2 wt% of PTFE of Example 3. Except for the above, a melt-kneaded product was prepared in the same manner as in Example 5. From this melt-kneaded product, a dried film having a thickness of 25 ⁇ m was obtained in the same manner as in Example 7.
  • the electrode layer On a PTFE sheet, 4 Ow t% of the platinum catalyst-carrying carbon (Tanaka Kikinzoku) and Ashipurekkusu (Ac ip 1 e X: registered trademark) solution (. EW910, 5 weight 0 /) platinum catalytic amount mixed solution of the After coating so as to be 1.0 to 1.5 mgZcm 2 , the electrode layer was obtained by drying at 130 ° C. for 1 hour. With the two electrode layers facing each other, the ion-exchange membrane was sandwiched between them, and pressed at 160 ° C. and a pressure of 50 kg / cm ”for 270 seconds to produce MEA.
  • the diffusion layer and MEA were assembled in a fuel cell single cell evaluation apparatus, and a fuel cell characteristic test was performed at 80 ° C. under normal pressure using hydrogen gas and air gas. Hydrogen was supplied at 80 ° C and air was supplied at 30 ° C.
  • the result of the characteristic test is shown in FIG. FIG. 2 also shows the characteristics test results when an ion exchange membrane was similarly prepared using the fluorine-based ion exchange resin precursor of Comparative Example 1, a fuel cell was assembled, and a characteristics test was performed. I have.
  • the fluorinated ion-exchange resin precursor composition according to the production method of the present invention has excellent mechanical strength due to uniform dispersion of PTFE and excellent melt moldability, a high-grade fluorinated ion-exchange resin precursor composition
  • the product sheet can be formed, which is particularly effective in improving the yield during mass production.

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Abstract

L'invention concerne une composition de précurseur de résine fluorée échangeuse d'ions obtenue par élimination de l'ingrédient liquide d'un mélange constitué d'une dispersion de précurseur de résine fluorée échangeuse d'ions et d'une dispersion de polytétrafluoroéthylène (PTFE).
PCT/JP2002/001197 2001-02-13 2002-02-13 Composition de precurseur de resine fluoree echangeuse d'ions Ceased WO2002072694A1 (fr)

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JP2008518424A (ja) * 2004-11-01 2008-05-29 ゼネラル・モーターズ・コーポレーション 燃料電池において用いられる高分子電解質膜フィルムを安定化させるための方法
WO2020105600A1 (fr) * 2018-11-19 2020-05-28 Ａｇｃ株式会社 Particules composites et membrane échangeuse d'ions
CN111533929A (zh) * 2019-02-07 2020-08-14 富士施乐株式会社 含氟树脂粒子、组合物、层状物、电子照相感光体、处理盒及图像形成装置
JP2020128521A (ja) * 2019-02-07 2020-08-27 富士ゼロックス株式会社 フッ素含有樹脂粒子、組成物、層状物、電子写真感光体、プロセスカートリッジ、および画像形成装置
JP2021181060A (ja) * 2020-05-19 2021-11-25 Ａｇｃエンジニアリング株式会社 中空糸膜製造用の複合粒子、中空糸膜、中空糸膜の製造方法

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CA2720687C (fr) * 2008-04-09 2013-03-26 Asahi Kasei E-Materials Corporation Composition de dispersion d'une resine a echange ionique contenant du fluor
US10586994B2 (en) 2013-07-02 2020-03-10 Asahi Kasei Kabushiki Kaisha Electrolyte solution and method for producing same, continuously dissolving facility, electrolyte membrane, electrode catalyst layer, membrane electrode assembly and fuel cell
JP2022014442A (ja) * 2020-07-06 2022-01-19 旭化成株式会社 重合体組成物およびイオン交換膜

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JP2008518424A (ja) * 2004-11-01 2008-05-29 ゼネラル・モーターズ・コーポレーション 燃料電池において用いられる高分子電解質膜フィルムを安定化させるための方法
WO2020105600A1 (fr) * 2018-11-19 2020-05-28 Ａｇｃ株式会社 Particules composites et membrane échangeuse d'ions
JPWO2020105600A1 (ja) * 2018-11-19 2021-10-14 Ａｇｃ株式会社 複合粒子およびイオン交換膜
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CN111533929A (zh) * 2019-02-07 2020-08-14 富士施乐株式会社 含氟树脂粒子、组合物、层状物、电子照相感光体、处理盒及图像形成装置
JP2020128521A (ja) * 2019-02-07 2020-08-27 富士ゼロックス株式会社 フッ素含有樹脂粒子、組成物、層状物、電子写真感光体、プロセスカートリッジ、および画像形成装置
JP2021181060A (ja) * 2020-05-19 2021-11-25 Ａｇｃエンジニアリング株式会社 中空糸膜製造用の複合粒子、中空糸膜、中空糸膜の製造方法

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